Metal Halide Perovskite Heterostructures: Blocking Anion Diffusion with Single-Layer Graphene

Matthew P. Hautzinger; Emily K. Raulerson; Steven P. Harvey; Tuo Liu; Daniel Duke; Xixi Qin; Rebecca A. Scheidt; Brian M. Wieliczka; Alan J. Phillips; Kenneth R. Graham; Volker Blum; Joseph M. Luther; Matthew C. Beard; Jeffrey L. Blackburn

doi:10.1021/jacs.2c12441

Metal Halide Perovskite Heterostructures: Blocking Anion Diffusion with Single-Layer Graphene

Matthew P. Hautzinger, Emily K. Raulerson, Steven P. Harvey, Tuo Liu, Daniel Duke, Xixi Qin, Rebecca A. Scheidt, Brian M. Wieliczka, Alan J. Phillips, Kenneth R. Graham, Volker Blum, Joseph M. Luther, Matthew C. Beard, Jeffrey L. Blackburn

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

The development of metal halide perovskite/perovskite heterostructures is hindered by rapid interfacial halide diffusion leading to mixed alloys rather than sharp interfaces. To circumvent this outcome, we developed an ion-blocking layer consisting of single-layer graphene (SLG) deposited between the metal halide perovskite layers and demonstrated that it effectively blocks anion diffusion in a CsPbBr₃/SLG/CsPbI₃ heterostructure. Spatially resolved elemental analysis and spectroscopic measurements demonstrate the halides do not diffuse across the interface, whereas control samples without the SLG show rapid homogenization of the halides and loss of the sharp interface. Ultraviolet photoelectron spectroscopy, DFT calculations, and transient absorbance spectroscopy indicate the SLG has little electronic impact on the individual semiconductors. In the CsPbBr₃/SLG/CsPbI₃, we find a type I band alignment that supports transfer of photogenerated carriers across the heterointerface. Light-emitting diodes (LEDs) show electroluminescence from both the CsPbBr₃ and CsPbI₃ layers with no evidence of ion diffusion during operation. Our approach provides opportunities to design novel all-perovskite heterostructures to facilitate the control of charge and light in optoelectronic applications.

Original language	English
Pages (from-to)	2052-2057
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	145
Issue number	4
DOIs	https://doi.org/10.1021/jacs.2c12441
State	Published - Feb 1 2023

Bibliographical note

Funding Information:
This work was supported by the Center for Hybrid Organic Inorganic Semiconductors for Energy (CHOISE), an Energy Frontier Research Center funded by the Office of Basic Energy Sciences, Office of Science within the U.S. Department of Energy through contract number DE-AC36-08G028308. The views expressed in the article do not necessarily represent the views of the DOE or the U.S. Government. T.L. and K.R.G. ackknowledge support from the National Science Foundation (award number OIA-1929131) for ultraviolet phoelectron spectroscopy measurements. D.D. carried out DFT simulations as part of a Research Experience for Undergraduate students program supported by the National Science Foundation (award numbers 2050900, 2050841, and 2050764 and ECCS-2025064). Any opinions, findings, and conclusions or recommendations expressed in this material do not necessarily reflect the views of the National Science Foundation. This research used resources of the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy (DOE) Office of Science User Facility operated under Contract no. DEAC02-05CH11231.

Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society.

ASJC Scopus subject areas

Catalysis
Chemistry (all)
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.2c12441

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Hautzinger, M. P., Raulerson, E. K., Harvey, S. P., Liu, T., Duke, D., Qin, X., Scheidt, R. A., Wieliczka, B. M., Phillips, A. J., Graham, K. R., Blum, V., Luther, J. M., Beard, M. C., & Blackburn, J. L. (2023). Metal Halide Perovskite Heterostructures: Blocking Anion Diffusion with Single-Layer Graphene. Journal of the American Chemical Society, 145(4), 2052-2057. https://doi.org/10.1021/jacs.2c12441

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abstract = "The development of metal halide perovskite/perovskite heterostructures is hindered by rapid interfacial halide diffusion leading to mixed alloys rather than sharp interfaces. To circumvent this outcome, we developed an ion-blocking layer consisting of single-layer graphene (SLG) deposited between the metal halide perovskite layers and demonstrated that it effectively blocks anion diffusion in a CsPbBr3/SLG/CsPbI3 heterostructure. Spatially resolved elemental analysis and spectroscopic measurements demonstrate the halides do not diffuse across the interface, whereas control samples without the SLG show rapid homogenization of the halides and loss of the sharp interface. Ultraviolet photoelectron spectroscopy, DFT calculations, and transient absorbance spectroscopy indicate the SLG has little electronic impact on the individual semiconductors. In the CsPbBr3/SLG/CsPbI3, we find a type I band alignment that supports transfer of photogenerated carriers across the heterointerface. Light-emitting diodes (LEDs) show electroluminescence from both the CsPbBr3 and CsPbI3 layers with no evidence of ion diffusion during operation. Our approach provides opportunities to design novel all-perovskite heterostructures to facilitate the control of charge and light in optoelectronic applications.",

author = "Hautzinger, {Matthew P.} and Raulerson, {Emily K.} and Harvey, {Steven P.} and Tuo Liu and Daniel Duke and Xixi Qin and Scheidt, {Rebecca A.} and Wieliczka, {Brian M.} and Phillips, {Alan J.} and Graham, {Kenneth R.} and Volker Blum and Luther, {Joseph M.} and Beard, {Matthew C.} and Blackburn, {Jeffrey L.}",

note = "Funding Information: This work was supported by the Center for Hybrid Organic Inorganic Semiconductors for Energy (CHOISE), an Energy Frontier Research Center funded by the Office of Basic Energy Sciences, Office of Science within the U.S. Department of Energy through contract number DE-AC36-08G028308. The views expressed in the article do not necessarily represent the views of the DOE or the U.S. Government. T.L. and K.R.G. ackknowledge support from the National Science Foundation (award number OIA-1929131) for ultraviolet phoelectron spectroscopy measurements. D.D. carried out DFT simulations as part of a Research Experience for Undergraduate students program supported by the National Science Foundation (award numbers 2050900, 2050841, and 2050764 and ECCS-2025064). Any opinions, findings, and conclusions or recommendations expressed in this material do not necessarily reflect the views of the National Science Foundation. This research used resources of the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy (DOE) Office of Science User Facility operated under Contract no. DEAC02-05CH11231. Publisher Copyright: {\textcopyright} 2023 The Authors. Published by American Chemical Society.",

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Hautzinger, MP, Raulerson, EK, Harvey, SP, Liu, T, Duke, D, Qin, X, Scheidt, RA, Wieliczka, BM, Phillips, AJ, Graham, KR, Blum, V, Luther, JM, Beard, MC & Blackburn, JL 2023, 'Metal Halide Perovskite Heterostructures: Blocking Anion Diffusion with Single-Layer Graphene', Journal of the American Chemical Society, vol. 145, no. 4, pp. 2052-2057. https://doi.org/10.1021/jacs.2c12441

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T1 - Metal Halide Perovskite Heterostructures

T2 - Blocking Anion Diffusion with Single-Layer Graphene

AU - Hautzinger, Matthew P.

AU - Raulerson, Emily K.

AU - Harvey, Steven P.

AU - Liu, Tuo

AU - Duke, Daniel

AU - Qin, Xixi

AU - Scheidt, Rebecca A.

AU - Wieliczka, Brian M.

AU - Phillips, Alan J.

AU - Graham, Kenneth R.

AU - Blum, Volker

AU - Luther, Joseph M.

AU - Beard, Matthew C.

AU - Blackburn, Jeffrey L.

N1 - Funding Information: This work was supported by the Center for Hybrid Organic Inorganic Semiconductors for Energy (CHOISE), an Energy Frontier Research Center funded by the Office of Basic Energy Sciences, Office of Science within the U.S. Department of Energy through contract number DE-AC36-08G028308. The views expressed in the article do not necessarily represent the views of the DOE or the U.S. Government. T.L. and K.R.G. ackknowledge support from the National Science Foundation (award number OIA-1929131) for ultraviolet phoelectron spectroscopy measurements. D.D. carried out DFT simulations as part of a Research Experience for Undergraduate students program supported by the National Science Foundation (award numbers 2050900, 2050841, and 2050764 and ECCS-2025064). Any opinions, findings, and conclusions or recommendations expressed in this material do not necessarily reflect the views of the National Science Foundation. This research used resources of the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy (DOE) Office of Science User Facility operated under Contract no. DEAC02-05CH11231. Publisher Copyright: © 2023 The Authors. Published by American Chemical Society.

PY - 2023/2/1

Y1 - 2023/2/1

N2 - The development of metal halide perovskite/perovskite heterostructures is hindered by rapid interfacial halide diffusion leading to mixed alloys rather than sharp interfaces. To circumvent this outcome, we developed an ion-blocking layer consisting of single-layer graphene (SLG) deposited between the metal halide perovskite layers and demonstrated that it effectively blocks anion diffusion in a CsPbBr3/SLG/CsPbI3 heterostructure. Spatially resolved elemental analysis and spectroscopic measurements demonstrate the halides do not diffuse across the interface, whereas control samples without the SLG show rapid homogenization of the halides and loss of the sharp interface. Ultraviolet photoelectron spectroscopy, DFT calculations, and transient absorbance spectroscopy indicate the SLG has little electronic impact on the individual semiconductors. In the CsPbBr3/SLG/CsPbI3, we find a type I band alignment that supports transfer of photogenerated carriers across the heterointerface. Light-emitting diodes (LEDs) show electroluminescence from both the CsPbBr3 and CsPbI3 layers with no evidence of ion diffusion during operation. Our approach provides opportunities to design novel all-perovskite heterostructures to facilitate the control of charge and light in optoelectronic applications.

AB - The development of metal halide perovskite/perovskite heterostructures is hindered by rapid interfacial halide diffusion leading to mixed alloys rather than sharp interfaces. To circumvent this outcome, we developed an ion-blocking layer consisting of single-layer graphene (SLG) deposited between the metal halide perovskite layers and demonstrated that it effectively blocks anion diffusion in a CsPbBr3/SLG/CsPbI3 heterostructure. Spatially resolved elemental analysis and spectroscopic measurements demonstrate the halides do not diffuse across the interface, whereas control samples without the SLG show rapid homogenization of the halides and loss of the sharp interface. Ultraviolet photoelectron spectroscopy, DFT calculations, and transient absorbance spectroscopy indicate the SLG has little electronic impact on the individual semiconductors. In the CsPbBr3/SLG/CsPbI3, we find a type I band alignment that supports transfer of photogenerated carriers across the heterointerface. Light-emitting diodes (LEDs) show electroluminescence from both the CsPbBr3 and CsPbI3 layers with no evidence of ion diffusion during operation. Our approach provides opportunities to design novel all-perovskite heterostructures to facilitate the control of charge and light in optoelectronic applications.

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Metal Halide Perovskite Heterostructures: Blocking Anion Diffusion with Single-Layer Graphene

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